Resin and article molded therefrom

ABSTRACT

The resin of the invention comprises both a phosphorus-containing residue having a bicycloalkyl structure and a specific divalent phenol residue. The invention provides a resin having excellent optical properties, which is colorless and transparent, has a high refractive index and is optically low dispersive, as well as its molded product.

TECHNICAL FIELD

The present invention relates to a resin excellent in opticalproperties, which is optically low dispersive and has a high refractiveindex, as well as its molded product.

BACKGROUND ART

As colorless and transparent materials, various materials have been usedin an optical lens, a functional optical film and a disk substrate,depending on various applications, and with rapid development in healthcare and electronics, functions and performance required of thematerials themselves become increasingly accurate and excellent.

In application to health care, an eyeglass lens can be mentioned, andfrom the viewpoint of thinning, light weight and fashion, activedevelopment of materials is made, and for advantages such as impactresistance, light weight etc., resin lenses come to account for 90% ofthe commercial eyeglass lenses at present.

The resin for conventional eyeglass lenses is divided roughly into 3kinds of resin, that is, CR39, acrylic resin and urethane resin, andmany resins have been developed and practically used to achieve lowdispersibility and high refraction. Because all of these resins arethermosetting, cast molding is used in molding thereof into opticallenses, but this method suffers from problems such as longpolymerization time and high production costs in a subsequent annealingprocess etc. Application of thermoplastic resin such as polycarbonate tolenses is advantageous in a significant reduction in production costswith good moldability, as compared with the thermosetting resin, but thethermoplastic resin applied to eyeglasses for eyesight correction ispoor in performance because of a low Abbe number (that is, highchromatic aberration due to high dispersibility) and relatively highoptical strain. A large number of thermoplastic resins having a higherrefractive index than that of polycarbonate are known, but have problemssuch as high dispersibility, easy coloration etc. and are thusproblematic for use in optical lenses.

Various resins containing a phosphorus-based functional group are known,and resins containing a phosphonate group in a main chain thereof arecalled polyphosphonates and vigorously studied for improvement infunctions such as flame retardance. With respect to many of such knownpolyphosphonate-based resins, there is no detailed knowledge of physicalproperties such as optical properties and physical properties, and thusthe present inventors synthesized such resins and evaluated physicalproperties thereof. As a result, these known polyphosphonate-basedresins are poor in physical properties or poor in refractive index andlight dispersibility.

In the Patent Document 1, the optical properties etc. of aphosphonate/carbonate copolymer are described in detail, and the opticalproperties thereof are improved as compared with those of conventionalresin. However, the light dispersibility (Abbe number) of the resindescribed in the patent application supra cannot be said to besatisfactory for use in optical lenses, so there is need a resin havinga high refractive index and a further high Abbe number.

-   Patent Document 1: European Patent Application No. 1270646A1

DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTIONSUMMARY OF INVENTION

In view of the foregoing background of the related art, the object ofthe present invention is to provide a resin having excellent opticalproperties, which is colorless and transparent, has a high refractiveindex and is optically low dispersive, as well as its molded product.

MEANS FOR SOLVING THE PROBLEMS

The present invention has the following means to solve the problem. Thatis, the resin of the present invention includes both aphosphorus-containing residue having a bicycloalkyl structure and adivalent phenol residue represented by the following general formula(1):

As used herein, the phosphorus-containing residue represents a residueof phosphonic acid, thiophosphonic acid, selenophosphonic acid,phosphonous acid or phosphoric acid. Two or more kinds of these residuesmay be contained in the resin. In the general formula (1), Rs areindependently selected from the group consisting of a hydrogen atom, aC1 to C20 aliphatic hydrocarbon group, a C1 to C20 aromatic hydrocarbongroup, a halogen atom and a nitro group. Each of p and q is an integersatisfying the equation: p+q=0 to 8. Y is a group selected from thegroup consisting of an alkylidene group, a branched chain-containingalkylidene group, a cycloalkylidene group and a branchedchain-containing cycloalkylidene group. Two or more kinds of divalentphenol residues different in R or Y may be contained in the resin.

Further, the present invention encompasses a molded product such as anoptical lens and film comprising the resin.

EFFECT OF THE INVENTION

According to the present invention, there can be provided a resin and amolded product having properties such as high refractive index and lowdispersibility.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention have previously found that the object describedabove, that is, the thermoplastic resin having excellent opticalproperties, which is colorless and transparent, has a high refractiveindex and is optically low dispersible can be obtained by introducing astructure having a pentavalent phosphorus atom, particularly aphosphonic acid structure, into a main chain of the polymer(EP-A-1270646), and the present inventors have made further extensiveexamination. As a result, they found that by introducing aphosphorus-containing residue having a bicyclo-structure into a mainchain of the polymer, the resulting resin can exhibit extremely higheroptical properties than by a general phosphonic acid structure having analkyl group, and the present invention was thereby arrived at.

Among optical properties, the refractive index depends on the degree ofpolarization inherent in an atomic group and the density of the atomicgroup, so various structures have been examined to improve the densityof an atomic group on a phosphorus atom. As a result, a benzene ornaphthalene ring having high carbon density has a high refractive index,but its structure consisting of SP2 carbons is unsatisfactory due to alow Abbe number. Accordingly, a bicycloalkyl structure containing alarge number of SP3 carbons in a smaller space was examined, and as aresult, this structure exhibited a surprisingly high refractive indexand high Abbe number. That is, the bicycloalkyl structure was revealedto be practically extremely effective.

From the viewpoint of incorporating a larger number of SP3 carbons perunit space, the bicycloalkyl structure is preferably a compact structurewherein the number of carbons constituting the ring is 12(bicyclododecane) or less, particularly 9 (bicyclononane) or less.

With respect to the bonding of the phosphorus atom to the bicycloalkylstructure, the phosphorus atom and the bicycloalkyl skeleton are mostpreferably bound directly to each other in order to incorporate a largernumber of SP3 carbons into the space thereof, but may be bound to eachother via an alkylene group such as a methylene group or an ethylenegroup. From the viewpoint of optical properties, thephosphorus-containing residue having a bicycloalkyl group is morepreferably a structure represented by the following general formula (2):

In the general formula (2), l, m and n independently represent aninteger of 1 to 4. When l, m and n are in this range, SP3 carbons can becontained in a large amount per unit space. l, m and n are morepreferably 1 to 3. X represents oxygen, sulfur, selenium or a pair ofnon-covalent electrons.

The position where the phosphorus atom is bound to the bicycloalkylstructure is arbitrary, and this bonding may be bridge-head or bridge.The substituent R′ is selected from the group consisting of a hydrogenatom, a C1 to C20 aliphatic hydrocarbon group, a C1 to C20 aromatichydrocarbon group and a halogen atom, and r is an integer of 0 to 4.When r is an integer of 2 or more, two or more kinds of differentsubstituents R′ may be contained in the same bicycloalkyl structure. Twoor more kinds of phosphorus-containing residues different in l, m, n, R′or X may be contained in the resin.

Particularly preferable structures of such bicycloalkyl groups includebicyclo[2,2,1]-1-heptyl(1-norbornyl),bicyclo[2,2,1]-2-heptyl(2-norbornyl),bicyclo[2,2,1]-7-heptyl(7-norbornyl), bicyclo[2,2,2]-1-octyl,bicyclo[2,2,2]-2-octyl, bicyclo[3,2,1]-2-octyl, bicyclo[3,2,2]-2-nonyl,bicyclo[4,2,2]-2-decanyl etc. These may be contained alone or incombination of plural kinds thereof. To regulate physical properties andthermal properties, the substituent R′ on the bicycloalkyl may beintroduced in such a range as not to deteriorate optical properties, butfrom the viewpoint of incorporation of a larger number of SP3 carbonsper unit space, the substituent R′ is preferably a compact structuresuch as a methyl group, an ethyl group or a halogen atom. From the sameviewpoint, the number (r) of the substituents is preferably 4 or less,more preferably 2 or less.

To regulate thermal, chemical or physical properties, the resin of thepresent invention can contain a phosphorus-containing residuerepresented by the following general formula (3) in addition to thephosphorus-containing residue represented by the general formula (2).

wherein R″ represents an organic group other than the bicycloalkyl grouprepresented by the general formula (2), and X′ represents oxygen,sulfur, selenium or a pair of non-covalent electrons.

The following relationship (I) is a relationship showing thecopolymerization fraction of the phosphorus-containing residuerepresented by the general formula (2) to the phosphonic acid residuerepresented by the general formula (3).1≧(a)/{(a)+(b)}≧0.05   (I)

That is, (a) represents the number of moles of the phosphorus-containingresidue represented by the general formula (2), and (b) represents thenumber of moles of the phosphorus-containing residue represented by thegeneral formula (3). When the mol fraction [(a){(a)+(b)}] of thephosphorus-containing residue represented by the general formula (2) isless than 0.05, the effect of the present invention, that is, the highAbbe number and high refractive index of the resin, is hardly obtained.The mol fraction [(a)/{(a)+(b)}] is preferably in the range of 0.25 ormore, more preferably 0.4 or more, still more preferably 0.6 or more.

Specific examples of the substituent R″ constituting thephosphorus-containing residue represented by the general formula (3)include groups such as phenyl, halo-substituted phenyl, methoxyphenyl,ethoxyphenyl, methyl, ethyl, isopropyl, cyclohexyl, vinyl, allyl,benzyl, aminoalkyl, hydroxyalkyl, halo-substituted alkyl, alkylsulfideetc. Specific examples of such phosphorus-containing residues includeresidues of methyl phosphonic acid, ethyl phosphonic acid, n-propylphosphonic acid, isopropyl phosphonic acid, n-butyl phosphonic acid,isobutyl phosphonic acid, t-butyl phosphonic acid, n-pentyl phosphonicacid, neopentyl phosphonic acid, cyclohexyl phosphonic acid, benzylphosphonic acid, chloromethyl phosphonic acid, dichloromethyl phosphonicacid, bromomethyl phosphonic acid, dibromomethyl phosphonic acid,2-chloroethyl phosphonic acid, 1,2-dichloroethyl phosphonic acid,2-bromoethyl phosphonic acid, 1,2-dibromoethyl phosphonic acid,3-chloropropyl phosphonic acid, 2,3-dichloropropyl phosphonic acid,3-bromopropyl phosphonic acid, 2,3-dibromopropyl phosphonic acid,2-chloro-1-methylethyl phosphonic acid, 1,2-dichloro-1-methylethylphosphonic acid, 2-bromo-1-methylethyl phosphonic acid,1,2-dibromo-1-methylethyl phosphonic acid, 4-chlorobutyl phosphonicacid, 3,4-dichlorobutyl phosphonic acid, 4-bromobutyl phosphonic acid,3,4-dibromobutyl phosphonic acid, 3-chloro-1-methylpropyl phosphonicacid, 2,3-dichloro-1-methylpropyl phosphonic acid,3-bromo-1-methylpropylphosphonic acid, 2,3-dibromo-1-methyl phosphonicacid, 1-chloromethylpropyl phosphonic acid,1-chloro-1-chloromethylpropyl phosphonic acid, 1-bromomethylpropylphosphonic acid, 1-bromo-1-bromomethylpropyl phosphonic acid,5-chloropentyl phosphonic acid, 4,5-dichloropentyl phosphonic acid,5-bromopentyl phosphonic acid, 4,5-dibromopentyl phosphonic acid,1-hydroxymethyl phosphonic acid, 2-hydroxyethyl phosphonic acid,3-hydroxypropyl phosphonic acid, 4-hydroxybutyl phosphonic acid,5-hydroxypentyl phosphonic acid, 1-aminomethyl phosphonic acid,2-aminoethyl phosphonic acid, 3-aminopropyl phosphonic acid,4-aminobutyl phosphonic acid, 5-aminopentyl phosphonic acid,methylthiomethyl phosphonic acid, methylthioethyl phosphonic acid,methylthiopropyl phosphonic acid, methylthiobutyl phosphonic acid,ethylthiomethyl phosphonic acid, ethylthioethyl phosphonic acid,ethylthiopropyl phosphonic acid, propylthiomethyl phosphonic acid,propylthioethyl phosphonic acid, butylthiomethyl phosphonic acid, phenylphosphonic acid, 4-chlorophenyl phosphonic acid, 3,4-dichlorophenylphosphonic acid, 3,5-dichlorophenyl phosphonic acid, 4-bromophenylphosphonic acid, 3,4-bromophenyl phosphonic acid, 3,5-bromophenylphosphonic acid, 4-methoxyphenyl phosphonic acid, 3,4-dimethoxyphenylphosphonic acid, 1-naphthyl phosphonic acid, 2-naphthyl phosphonic acid,5,6,7,8-tetrahydro-2-naphthyl phosphonic acid,5,6,7,8-tetrahydro-1-naphthyl phosphonic acid, benzyl phosphonic acid,4-bromophenylmethyl phosphonic acid, 3,4-dibromophenylmethyl phosphonicacid, 3,5-dibromophenylmethyl phosphonic acid, 2-phenylethyl phosphonicacid, 2-(4-bromophenyl)ethyl phosphonic acid, 2-(3,4-dibromophenyl)ethylphosphonic acid, 2-(3,5-dibromophenyl)ethyl phosphonic acid,3-phenylpropyl phosphonic acid, 3-(4-bromophenyl)propyl phosphonic acid,3-(3,4-dibromophenyl)propyl phosphonic acid, 3-(3,5-dibromophenyl)propylphosphonic acid, 4-phenylbutyl phosphonic acid, 4-(4-bromophenyl)butylphosphonic acid, 4-(3,4-dibromophenyl)butyl phosphonic acid,4-(3,5-dibromophenyl)butyl phosphonic acid, 2-pyridyl phosphonic acid,3-pyridyl phosphonic acid, 4-pyridyl phosphonic acid,1-pyrrolidinomethyl phosphonic acid, 1-pyrrolidinoethyl phosphonic acid,1-pyrrolidinopropyl phosphonic acid, 1-pyrrolidinobutyl phosphonic acid,pyrrole-1-phosphonic acid, pyrrole-2-phosphonic acid,pyrrole-3-phosphonic acid, thiophene-2-phosphonic acid,thiophene-3-phosphonic acid, dithiane-2-phosphonic acid,trithiane-2-phosphonic acid, furan-2-phosphonic acid, furan-3-phosphonicacid, vinyl phosphonic acid, and allyl phosphonic acid. A thiophosphonicacid residue wherein X′ is a sulfur atom or a phosphonous acid residuewherein X′ is a pair of non-covalent electrons, represented by thegeneral formula (3), can also be mentioned. These can be contained aloneor as a mixture of plural kinds thereof.

To regulate thermal, chemical and physical properties or moldability,the resin of the present invention can contain an other acid residue.Examples of such other acid residues include hetero-acid residues ofsilicon acid, sulfuric acid, boric acid etc., a carbonic acid residueand a divalent carboxylic acid residue. From the viewpoint of chemicalstability etc., a carbonic acid residue and a divalent carboxylic acidresidue are preferable. These can be contained alone or a mixture ofplural kinds thereof.

The other acid residue such as a hetero-acid residue, a carbonic acidresidue or a dicarboxylic acid residue can be contained in the resin ofthe present invention in the range of the copolymerization fraction ofthe relationship (II) below, to regulate thermal, chemical and physicalproperties or moldability.

The following relationship (II) is a relationship showing thecopolymerization fraction of the total of the phosphorus-containingresidue represented by the general formula (2) and thephosphorus-containing residue represented by the general formula (3) tothe other acid residues.1≧(c)/{(c)+(d)}≧0.05   (II)

That is, (c) is the number of moles in total of thephosphorus-containing residue represented by the general formula (2) andthe phosphorus-containing residue represented by the general formula (3)(number of moles of the total phosphorus-containing residues), and (d)is the number of moles of the other acid residues in total. When the molfraction of the total phosphorus-containing residues is less than 0.05,the high Abbe number of the resin is not exhibited, and the effect ofthe present invention is hardly obtained. From the viewpoint of theabove effect, the mol fraction of the total phosphorus-containingresidues [(c)/{(c)+(d)}] is preferably in the range of 0.25 or more,more preferably 0.5 or more, still more preferably 0.75 or more.

In the particularly preferably selected carboxylic acid residue anddivalent carboxylic acid residue, the divalent carboxylic acidconstituting the divalent carboxylic acid residue includes an aromaticdicarboxylic acid, a linear aliphatic dicarboxylic acid, an alicyclicdicarboxylic acid etc., and specific examples include terephthalic acid,isophthalic acid, biphenyl dicarboxylic acid, dicarboxy diphenylsulfone, malonic acid, succinic acid, adipic acid, cyclohexanedicarboxylic acid, dodecane diacid, sebacic acid etc. These residuesincluding the carbonic acid residue may be contained alone or as amixture of plural kinds thereof.

Among the divalent carboxylic acid residues, aliphatic divalentcarboxylic acid residues are particularly preferable, and C8 to C20divalent carboxylic acid residues are more preferable, from theviewpoint of thermal properties and physical properties of the resin.Specific examples include cyclohexane dicarboxylic acid, dodecane diacidand sebacic acid.

From the viewpoint of optical properties, heat resistance and physicalproperties, the divalent phenol residue is preferably a structural unitwhose starting material is aromatic bisphenol, particularly preferably adivalent phenol residue represented by the following general formula(1):

wherein Rs are independently selected from the group consisting of ahydrogen atom, a C1 to C20 aliphatic hydrocarbon group, a C1 to C20aromatic hydrocarbon group, a halogen atom and a nitro group. Each of pand q is an integer satisfying the equation: p+q=0 to 8. Y is a groupselected from the group consisting of an alkylidene group, a branchedchain-containing alkylidene group, a cycloalkylidene group and abranched chain-containing cycloalkylidene group. Two or more kinds ofdivalent phenol residues different in R or Y may be contained in theresin.

Specific examples of divalent phenols constituting the divalent phenolresidues represented by the general formula (1) include2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)cycloheptane,1,1-bis(4-hydroxyphenyl)cyclooctane, 1,1-bis(4-hydroxyphenyl)cyclodecane1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane, 1,1-bis(4-hydroxyphenyl)-2-methyl propane,1,1-bis(3-methyl-4-hydroxyphenyl)cyclohexane, bisphenol fluorene,1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)-2-methyl propane,4,4′-[1,4-phenylene-bis(2-propylidene)]-bis(2-methylphenol),1,1-bis(3-phenyl-4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3-methyl-butane,1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(3-methyl-4-hydroxyphenyl)cyclopentane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, terpene diphenol-, 1,1-bis(3-tert-butyl-4-hydroxyphenyl)cyclohexane,1,1-bis(2-methyl-4-hydroxy-5-tert-butylphenyl)-2-methyl propane,1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5,5-tetramethyl-cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,4-trimethyl-cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3-dimethyl-5-ethyl-cyclohexane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclopentane,1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(3,5-diphenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(3-methyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(3-phenyl-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,1,1-bis(3,5-dichloro-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,9,9-bis(4-hydroxyphenyl)fluorene,9,9-bis(3,5-dimethyl-4-hydroxyphenyl)fluorene,1,1-bis(3,5-dibromo-4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane,α,α′-bis(4-hydroxyphenyl)-1,4-diisopropyl benzene etc. These can becontained alone or as a mixture of plural kinds thereof. These divalentphenols can be used depending on the performance of the resulting resin.

From the viewpoint of optical properties, heat resistance and physicalproperties, among these divalent phenols, particularly preferabledivalent phenols are selected from those represented by the generalformula (1) wherein Y is a branched chain-containing alkylidene group, acycloalkylidene group, a branched chain-containing cycloalkylidene groupand a bicycloalkylidene group, and particularly preferable examples are1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)cyclooctane,1,1-bis(4-hydroxyphenyl)cyclododecane 1,1-bis(4-hydroxyphenyl)-4-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropyl cyclohexane,2,2-bis(4-hydroxyphenyl)-4-methyl pentane,1,1-bis(4-hydroxyphenyl)-3,3,5-trimethyl cyclohexane, and2,2-bis(4-hydroxyphenyl)norbornane.

Further, dihydroxy benzene can be used in such a range that the effectof the present invention is not deteriorated. The dihydroxy benzeneincludes resorcinol, hydroquinone, 1,2-dihydroxy benzene etc. These maybe contained alone or as a mixture of plural kinds thereof.

The resin of the present invention is not always necessary to be linear,and can be copolymerized with polyvalent phenols, depending on theperformance of the resulting resin. Specific examples of such polyvalentphenols include tris(4-hydroxyphenyl) methane,4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]bisphenol,2,3,4,4′-tetrahydroxy benzophenone,4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,tris(3-methyl-4-hydroxyphenyl)methane,4-[bis(3-methyl-4-hydroxyphenyl)methyl]-2-methoxy phenol,4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy phenol,1,1,1-tris(4-hydroxyphenyl)ethane,1,1,1-tris(3-methyl-4-hydroxyphenyl)ethane,1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane,tris(3-methyl-4-hydroxyphenyl)methane,tris(3,5-dimethyl-4-hydroxyphenyl)methane,2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methyl phenol,4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2-dihydroxy benzene,2-[bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)methyl]-phenol,4-[bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)methyl]-1,2-dihydroxybenzene, 4-methylphenyl-1,2,3-trihydroxy benzene,4-[(4-hydroxyphenyl)methyl]-1,2,3-trihydroxy benzene,4-[1-(4-hydroxyphenyl)-1-methyl-ethyl]-1,3-dihydroxy benzene,4-[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2,3-trihydroxy benzene,1,4-bis[1-bis(3,4-dihydroxyphenyl)-1-methyl-ethyl]benzene,1,4-bis[1-bis(2,3,4-trihydroxyphenyl)-1-methyl-ethyl]benzene,2,4-bis[(4-hydroxyphenyl)methyl]-1,3-dihydroxy benzene,2-[bis(3-methyl-4-hydroxyphenyl)methyl]phenol,4-[bis(3-methyl-4-hydroxyphenyl)methyl]phenol,2-[bis(2-methyl-4-hydroxyphenyl)methyl]phenol,4-[bis(3-methyl-4-hydroxyphenyl)methyl]-1,2-dihydroxy benzene,4-[bis(4-hydroxyphenyl)methyl]-2-ethoxy phenol,2-[bis(2,3-dimethyl-4-hydroxyphenyl)methyl]phenol,4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]phenol,3-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]phenol,2-[bis(2-hydroxy-3,6-dimethylphenyl)methyl]phenol,4-[bis(2-hydroxy-3,6-dimethylphenyl)methyl]phenol,4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy phenol,3,6-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2-dihydroxy benzene,4,6-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2,3-trihydroxy benzene,2-[bis(2,3,6-trimethyl-4-hydroxyphenyl)methyl]phenol,2-[bis(2,3,5-trimethyl-4-hydroxyphenyl)methyl]phenol,3-[bis(2,3,5-trimethyl-4-hydroxyphenyl)methyl]phenol,4-[bis(2,3,5-trimethyl-4-hydroxyphenyl)methyl]phenol,4-[bis(2,3,5-trimethyl-4-hydroxyphenyl)methyl]-1,2-dihydroxy benzene,3-[bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)methyl]phenol,4-[bis(2-methyl-4-hydroxy-5-cyclohexylphenyl) methyl]phenol,4-[bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)methyl]-2-methoxy phenol,2,4,6-[tris(4-hydroxyphenylmethyl)-1,3-dihydroxy benzene,1,1,2,2-tetra(3-methyl-4-hydroxyphenyl)ethane,1,1,2,2-tetra(3,5-dimethyl-4-hydroxyphenyl)ethane,1,4-[[bis(4-hydroxyphenyl)methyl]]benzene,1,4-di[bis(3-methyl-4-hydroxyphenyl)methyl]benzene,1,4-di[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]benzene,4-[1,1-bis(4-hydroxyphenyl)ethyl]aniline,(2,4-dihydroxyphenyl)(4-hydroxyphenyl)ketone,2-[bis(4-hydroxyphenyl)methyl]phenol, 1,3,3-tri(4-hydrophenyl)butaneetc. These may be contained alone or as a mixture of plural kindsthereof.

The Abbe number (νd) of the resin of the present invention is preferably32 or more. The Abbe number (νd) is one indicator showing the degree oflight dispersion of an optical substance and defined generally by thefollowing equation (III):Abbe number (νi d)=(nd−1)/(nf−nc)   (III)wherein nd is a d-line (wavelength 587.6 nm) refractive index, nf is a fline (wavelength 486.1 nm) refractive index, and nc is a c line(wavelength 656.3 nm) refractive index.

That is, a larger Abbe number is indicative of lower dispersion. Forexample, the Abbe number of the resin used in an eyeglass lens ispreferably 33 or more, more preferably 34 or more.

The refractive index at each wavelength is a value inherent in eachsubstance, and accordingly the Abbe number is a value inherent in eachsubstance. That is, the refractive index does not vary depending on itsmeasurement method, and a measurement method suitable for the shape ofits molded product can be selected. A more highly accurate measurementmethod is preferable, and for example there is a minimum deviationmethod.

Usually, there is a negative correlation between the Abbe number andrefractive index, so both the properties are hardly simultaneouslyimproved. The resin of the present invention is a resin having a highAbbe number while maintaining a refractive index equal to, or higherthan, that of conventional polycarbonate.

The resin of the present invention preferably has a high refractiveindex for use in optical uses, particularly lenses. The refractive index(nd), measured with d line (wavelength: 587.6 nm), is preferably 1.58 ormore, more preferably 1.59 or more.

However, there is a negative correlation between the Abbe number andrefractive index as described above. Even if its refractive index ishigh, a resin is not preferable for optical uses, particularly lensesinsofar as its Abbe number is too low. That is, there is a suitablerange for the respective characteristic values. It is particularlyimportant for use in lenses that the value represented by the formula(IV) with respect to the Abbe number (νd) and d line refractive index(nd) is 210.5 or more. The formula (IV) is a formula showing a range inwhich both the Abbe number (νd) and d line refractive index (nd) arepreferable. The value represented by the formula (IV) is preferablyhigher, more preferably 211 or more.(νd)+112×(nd)   (IV)

Hereinafter, the method of producing the resin of the present inventionand the method of molding the same are described.

As a polymer precursor from which the phosphorus-containing residuehaving bicycloalkyl, the corresponding acid halide or ester is used. Asthe method of synthesizing it, methods involving Diels-Alder reaction ofa phosphorus-containing vinyl derivative with various cyclic dienecompounds and subsequent hydrogenation reaction are known (Phosphorus,Sulfur and Silicon and Related Elements, No. 123, p. 35 (1997)), andsuch known methods can be used. That is, a bicycle[2,2,1]-2-heptylphosphonic acid derivative, for example, can be obtained by Diels-Alderreaction of cyclopentadiene with a vinyl phosphonic acid derivative andsubsequent hydrogenation reaction, and a bicycle[2,2,2]-2-octylphosphonic acid derivative can be obtained by Diels-Alder reaction ofcyclohexadiene with a vinyl phosphonic acid derivative and subsequenthydrogenation reaction.

The method of producing the resin of the present invention includes asolution polymerization method which involves reacting an acid halidewith a divalent phenol in an organic solvent (A. Conix, Ind. Eng. Chem.51 147, 1959; JP-B 37-5599), a melt polymerization method which involvesheating an acid halide and a divalent phenol in the presence of acatalyst such as magnesium chloride, a melt polymerization method whichinvolves heating a divalent acid and a divalent phenol in the presenceof diallyl carbonate (JP-B 38-26299), an interfacial polymerizationmethod that involves mixing a divalent acid halide dissolved in awater-incompatible organic solvent and a divalent phenol dissolved in anaqueous alkali solution (W. M. EARECKSON, J. Poly. Sci. XL399, 1959;JP-B 40-1959) etc., among which the solution polymerization method ispreferably used. By way of example, the resin of the present inventioncan be obtained by the solution polymerization method which includesmixing a phosphonic acid derivative as a precursor molecule, in the caseof a phosphonic acid residue, with a divalent phenol in the presence ofa base such as triethylamine and then adding a precursor molecule of acarbonic acid residue or a divalent carboxylic acid, such as phosgene,triphosgene or a divalent carboxylic acid derivative, followed bycondensation polymerization thereof. As the phosphonic acid derivative,carbonate derivative or divalent carboxylic acid derivative, its halide,acid anhydride, ester etc. are used, and their type and the order inwhich these are allowed to act on the divalent phenol are notparticularly limited. The method of regulating the molecular weight ofthe resin of the present invention can be carried out by adding amonofunctional substance at the time of polymerization. Themonofunctional substance used as a molecular-weight regulator referredto herein includes monovalent phenols such as phenol, cresol,p-tert-butyl phenol etc. and monovalent acid chlorides such as benzoicchloride, methane sulfonyl chloride, phenyl chloroformate etc.

Various antioxidants based on hindered phenol, hindered amine,thioether, or phosphorus can be added to the resin of the presentinvention in such a range that its properties are not deteriorated.

The resin according to the present invention can be used as a moldingmaterial after blending with another resin in such range that thedesired effect is not deteriorated. Examples of such resin blendedinclude polycarbonate, polyethylene, polypropylene, polystyrene, ABSresin, polymethylmethacrylate, polytrifluoroethylene,polytetrafluoroethylene, polyacetal, polyphenylene oxide, polybutyleneterephthalate, polyethylene terephthalate, polyamide, polyimide,polyamide imide, polyether imide, polysulfone, polyether sulfone,p-oxybenzoyl-based polyester, polyarylate, polysulfide etc.

The resin of the present invention has high solubility in an organicsolvent, and such solvent includes methylene chloride, chloroform,1,1,2,2-tetrachloroethane, 1,2-dichloroethane, tetrahydrofuran,1,4-dioxane, toluene, xylene, γ-butyrolactone, benzyl alcohol,isophorone, chlorobenzene, dichlorobenzene, hexafluoroisopropanol etc.The resin of the present invention is non-crystalline, and whether theresin is non-crystalline can be determined by confirming whether itsmelting point is present or not by a known method, for example bydifferential scanning calorimetry (DSC) or dynamic viscoelasticitymeasurement.

For the method of analyzing the constituent components in the resin ofthe present invention, a method of using a nuclear magnetic resonancespectrum is preferable, and particularly a substituent on the phosphorusatom in the phosphorus-containing residue is analyzed preferably byproton or phosphorus atom nuclear magnetic resonance. When the accuracyof identification of the resin itself by its spectrum is notsatisfactory, the resin of the present invention is hydrolyzed with analkali or the like and decomposed into monomer components, and then eachcomponent can be quantitatively or qualitatively analyzed. For example,the resin of the present invention is treated with an excess of a strongbase such as an alkali metal alcoholate in an anhydrous alcohol, wherebythe divalent phenol residue is decomposed into a divalent phenol, andeach acid residue is decomposed into an ester corresponding to thealcoholate ion. These are low-molecular products and can thus bequantified and separated by high-performance liquid chromatography andthen subjected to detailed structural analysis by nuclear magneticresonance spectrum etc.

The method of obtaining a molded product such as a lens from the resinof the present invention is not particularly limited, and may be a knownmethod, for example injection molding, press molding, compressionmolding, transfer molding, laminate molding and extrusion molding. Inmolding into a film, a solution film manufacturing method and a meltextrusion film manufacturing method can be mentioned, and particularlysolution film manufacturing is preferably used. In the solution filmmanufacturing method, the above-mentioned organic solvent can besuitably used, and the organic solvent used in molding is preferably ahalogen-containing solvent, more preferably methylene chloride.

The resin of the present invention is thermoplastic and thus easilymoldable. Its lens has a high Abbe number and high refractive index, andcan thus provide an optically excellent lens with low chromaticaberration. The film using the resin of the present invention hasexcellent optical properties (colorless, transparent and lowlight-dispersible), has excellent affinity for various solvents, is thusexcellent in surface processability, and can provide an excellentfunctional film or base film in high-functional film members required inliquid crystal displays etc.

EXAMPLES

Hereinafter, specific embodiments of the present invention are describedby reference to the Examples, but the present invention is not limitedthereto.

Synthesis and evaluation of the resin were conducted by the followingmethods.

[Synthesis]

According to the formulations shown in Table 1, each resin in Examples 1to 16 and Comparative Examples 1 to 3was synthesized. The synthesismethod is described by reference to a method of synthesizing theformulation in Example 11.

In a nitrogen atmosphere, a starting material A(1,1-bis(4-hydroxyphenyl)cyclohexane, 80 mmol) and triethyl amine (168mmol) were mixed with methylene chloride (40 ml) and stirred undercooling on ice. A solution (5 mol/L) of a starting material B(2-norbornyl phosphonic dichloride, 28 mmol) in methylene chloride wasadded dropwise to the solution over 15 minutes, and thereafter themixture was stirred at room temperature for 60 minutes. Subsequently, asolution (5 mol/L) of a starting material C (phenyl phosphonicdichloride, 36 mmol) in methylene chloride was added thereto dropwiseover 15 minutes, and thereafter the mixture was stirred at roomtemperature for 60 minutes. Further, a solution (5 mol/L) of a startingmaterial D (sebacic dichloride, 8 mmol) in methylene chloride was addedthereto dropwise over 15 minutes, and thereafter the mixture was stirredat room temperature for 60 minutes. Thereafter, a solution (0.6 mol/L)of triphosgene (8 mmol in terms of phosgene) in methylene chloride wasadded thereto dropwise over 15 minutes, and thereafter the mixture wasstirred at room temperature for 60 minutes. Subsequently, the reactionsolution was passed through a filter paper having a pore diameter of 0.5μm to remove solid components, and the filtrate was washed several timeswith a mixed solution of 80 ml of 0.1 N aqueous hydrochloric acid and300 ml purified water. Thereafter, an organic layer was separatedtherefrom, then re-precipitated by introducing it into 2000 ml ethanol,and filtered to collect a polymer. The formed solid polymer was washedwith (1) 1000 ml ethanol, (2) 1000 ml mixed solution ofwater/ethanol=1/1, and (3) 1000 ml water in this order, and then driedto give the objective resin powder in 95% yield.

The resins in the other Examples and Comparative Examples weresynthesized in the same manner as above except that the amount of thestarting materials added were changed so as to give each formulationshown in Table 1.

[Molding]

The resulting resin powder was molded and evaluated in the followingmethods. That is, a plate-shaped molded product was produced by pressmolding. The resulting resin powder was introduced into a mold heated at250° C. higher than the glass transition temperature of the resin, andthen pressurized at a pressure of 2 tons, and the mold was cooled andpartitioned, whereby a disk-shaped resin molded product of φ30 mm and 3mm in thickness was obtained.

For measurement of optical properties, the resulting resin moldedproduct was cut to produce two faces perpendicular to each other, andboth the faces were mirror-finished by polishing with a buff.

Alternatively, the resulting resin powder can be formed into a film bythe following method and measured for refractive index. That is, in thecase of solution casting film manufacturing, the resin is dissolved inchloroform to prepare a dope having a polymer solids content of 5% byweight. This dope was used to form a film on a glass plate and dried at40° C. for 12 hours under vacuum and then at 100° C. or more at normalpressures for 2 hours to give a cast film.

[Molecular Weight]

The resin powder was dissolved in chloroform to form 0.2 wt % solution,which was then measured by GPC (gel permeation chromatography) [GPC8020manufactured by Tosoh], to determine the number-average molecular weight(Mn). The molecular weight was determined using polystyrene as thestandard.

[Thermal properties: Glass Transition Point]

The glass transition temperature was determined by DSC (SSC5200manufactured by Seiko Instruments Inc.).

[Optical Properties]

The Abbe number and refractive index were measured in the followingmethod. That is, the molded product in the case of a plate form wasevaluated by a refractometer (KPR-2 manufactured by Kalnew Kogyo Co.,Ltd.), and the d line (wavelength: 587.6 nm) refractive index (nd) andthe Abbe number (νd) determined by the formula (III) were measured. Themolded product formed into a thin film was measured by an Abberefractometer (4T manufactured by Atago Co., Ltd.).

The properties of each resin in the Examples and Comparative Examplesare shown in Table 2. TABLE 1 Table 1 General formula (2) Generalformula (3) General formula (1) Co- Co- Monomer Monomer polymerizationMonomer polymerization R Y name X R′ l m n name ratio (%) X′ R″ nameratio (%) Examples 1 H c-hex M1 O H 1 2 2 M3 100 — — — — 2 H c-hex M1 OH 1 2 2 M3 80 O Ph M6 20 3 H c-hex M1 O H 1 2 2 M3 60 O Ph M6 40 4 Hc-hex M1 O H 1 2 2 M3 75 — — — — 5 H c-hex M1 O H 1 2 2 M3 60 — — — — 6H c-hex M1 O H 1 2 2 M3 70 O c-hex M7 15 7 H c-hex M1 O H 1 2 2 M3 50 —— — — 8 H c-hex M1 O H 1 2 2 M3 45 — — — — 9 H c-hex M1 O H 1 2 2 M3 40— — — — 10 H c-hex M1 O H 1 2 2 M3 5 O Ph M6 45 11 H c-hex M1 O H 1 2 2M3 35 O Ph M6 45 12 H c-hex M1 S H 1 2 2 M4 40 — — — — 13 H c-hex M1 S H1 2 2 M4 75 — — — — 14 H c-hex M1 O H 1 2 3 M5 80 — — — — 15 H i-pro M2O H 1 2 2 M3 15 O Ph M6 65 16 H i-pro M2 O H 1 2 2 M3 40 O Ph M6 40Comparative 1 H c-hex M1 — — — — — — — O Ph M6 75 Examples 2 H c-hex M1— — — — — — — — — — — 3 H c-hex M1 — — — — — — — O c-hex M7 100 Y:c-hex: cyclohexylidenei-pro: isopropylideneMonomer name:M1: 1,1-bis(4-hydroxyphenyl) cyclohexaneM2: 2,2-bis(4-hydroxyphenyl) propaneM3: 2-norbornyl phosphonic dichlorideM4: 2-norbornyl thiophosphonic dichlorideM5: 2-bicyclo[3.2.1]octyl phosphonic dichlorideM6: phenyl phosphonic dichlorideM7: cyclohexyl phosphonic dichlorideM8: dodecane diacid dichloride

TABLE 2 Table 1 (following the previous table) Divalent carboxylic acidCarbonic acid Copolymerization Copolymerization Monomer ratio Monomerratio name (%) name (%) a/a + b c/c + d Examples 1 — — — — 1 1 2 — — — —0.8 1 3 — — — — 0.6 1 4 — — M10 25 1 0.75 5 — — M10 40 1 0.6 6 — — M1015 0.82 0.85 7 M8 10 M10 40 1 0.5 8 M8 15 M10 40 1 0.45 9 M8 20 M10 40 10.4 10 M8 15 M10 35 0.1 0.5 11 M9 10 M10 10 0.44 0.8 12 — — M10 60 1 0.413 — — M10 25 1 0.75 14 M9 10 M10 10 1 0.8 15 M9 10 M10 10 0.19 0.8 16 —— M10 20 0.5 0.8 Comparative 1 — — M10 25 0 0.75 Examples 2 — — M10 100 — 0 3 — — — — 0 1Monomer name:M9: sebacic dichlorideM10: triphosgene (its copolymerization ratio is expressed in terms ofphosgene)

TABLE 3 Table 2 Molecular Vd + Tg(° C.) weight nd vd 112 * nd Examples 1134 31000 1.582 36.1 213.284 2 131 35000 1.590 35.0 213.080 3 128 380001.594 33.9 212.428 4 146 51000 1.588 34.8 212.656 5 153 53000 1.590 34.0212.080 6 138 52000 1.586 35.4 213.032 7 142 58000 1.585 34.2 211.720 8135 57000 1.583 34.5 211.796 9 127 58000 1.581 35.0 212.072 10 122 550001.597 32.1 210.964 11 123 53000 1.596 33.2 211.952 12 164 45000 1.59632.8 211.552 13 162 41000 1.604 33.2 212.848 14 140 38000 1.587 36.0213.744 15 108 42000 1.593 32.1 210.516 16 132 48000 1.587 32.8 210.544Comparative 1 140 48000 1.603 30.9 210.436 Examples 2 183 59000 1.59729.9 208.764 3 136 38000 1.578 36.3 213.036

As can be seen from Comparative Examples 1 to 3, the highly refractive,thermoplastic resins such as conventional polyposphoate resin ormodified polycarbonate resin have an Abbe number of less than 32 or arefractive index of less than 1.58, and are unsatisfactory for opticaluses, particularly in eyeglass lenses. On the other hand, it appearsthat the resins in Examples 1 to 16 are excellent thermoplastic opticalresins having both high Abbe number and high refractive index.

INDUSTRIAL APPLICABILITY

According to the present invention, there can be provided a resin havingproperties such as high refractive index and low dispersibility. Theresin of the present invention can be used not only in various fieldssuch as general-purpose molded products and films but also inparticularly lenses or optical films thereby further demonstrating itsfurther excellent effect.

1. A resin comprising both a phosphorus-containing residue having abicycloalkyl structure, said phosphorus-containing residue representinga residue selected from residues of phosphonic acid, thiophosphonicacid, selenophosphonic acid, phosphonous acid and phosphoric acid, and adivalent phenol residue represented by the following general formula(1):

wherein Rs are independently selected from the group consisting of ahydrogen atom, a C1 to C20 aliphatic hydrocarbon group, a C1 to C20aromatic hydrocarbon group, a halogen atom and a nitro group; each of pand q is an integer satisfying the equation: p+q=0 to 8; and Y is agroup selected from the group consisting of an alkylidene group, abranched chain-containing alkylidene group, a cycloalkylidene group anda branched chain-containing cycloalkylidene group.
 2. The resinaccording to claim 1, wherein the phosphorus-containing residue having abicycloalkyl structure is represented by the following general formula(2):

wherein 1, m and n independently represent an integer of 1 to 4, Xrepresents oxygen, sulfur, selenium or a pair of non-covalent electrons;the substituent R′ is selected from the group consisting of a hydrogenatom, a C1 to C20 aliphatic hydrocarbon group, a C1 to C20 aromatichydrocarbon group and a halogen atom; and r is an integer of 0 to
 4. 3.The resin according to claim 2, comprising: the phosphorus-containingresidue represented by the general formula (2); a phosphorus-containingresidue represented by the following general formula (3):

wherein R″ represents an organic group other than the bicycloalkyl grouprepresented by the general formula (2), and X′ represents oxygen,sulfur, selenium or a pair of non-covalent electrons; and the divalentphenol residue represented by the general formula (1), wherein the molfraction of the phosphorus-containing residue represented by the generalformula (2) and the phosphorus-containing residue represented by thegeneral formula (3) satisfies the following relationship (I):1≧(a)/{(a)+(b)}≧0.05   (I) wherein (a) represents the number of moles ofthe phosphorus-containing residue having a bicycloalkyl structure, and(b) represents the number of moles of the phosphorus-containing residuerepresented by the general formula (3).
 4. The resin according to claim3, which comprises the phosphorus-containing residue represented by thegeneral formula (2), the phosphorus-containing residue represented bythe general formula (3) below, the divalent phenol residue representedby the general formula (1), and other acid residues, wherein the molfraction of all the phosphorus-containing residues and the other acidresidues satisfies the following relationship (II):1≧(c)/{(c)+(d)}≧0.05   (II) wherein (c) represents the number of molesof all the phosphorus-containing residues in total and (d) representsthe number of moles of the other acid residues in total.
 5. The resinaccording to claim 4, wherein the other acid residues contain a carbonicacid residue and/or a divalent carboxylic acid residue.
 6. The resinaccording to claim 5, wherein the divalent carboxylic acid residue is analiphatic dicarboxylic acid residue.
 7. The resin according to claim 6,wherein the number of carbons in the aliphatic dicarboxylic acid residueis 8 or more.
 8. The resin according to claim 1, wherein the Abbe number(νd) that is an indicator of the light dispersibility of the resin andrepresented by the equation (III) is 32 or more:Abbe number (νd)=(nd−1)/(nf−nc)   (III) wherein nd is a d line(wavelength 587.6 nm) refractive index, nf is a f line (wavelength 486.1nm) refractive index, and nc is a c line (wavelength 656.3 nm)refractive index.
 9. The resin according to claim 1, wherein the Abbenumber (νd) as an indicator of the light dispersibility of the resin andthe d line (nd) refractive index of the resin are 1.58 or more, and thevalue represented by the following formula (IV) is 210.5 or more,(νd)+112×(nd)   (IV)
 10. A molded product comprising the resin accordingto claim
 1. 11. An optical lens comprising the molded product accordingto claim
 10. 12. A film comprising the molded product according to claim10.